DE3938918A1 - BLENDS WITH SYNERGISTIC PROPERTIES - Google Patents

Abstract

Compsns. of formula (I) contain as active components (1) polymer (P1) obtd. by reacting epihalohydrin of formula (II) or precursor of (II) with a polyalkylenepolyamine of formula R3R3aN-(CH2)2-3-NH2 (III); (2) specified type of water-sol. homo- or co-polymer (P2); and (3) textile auxiliary (T) which is reaction mixt., opt. neutralised with acid, obtd. by (i) reacting (II) with ammonia then post-reacting with (II), or (ii) reacting (II) with methylamine or dimethylamine to form polymer of mol. wt. (as base) 500-10,000. (P2) is (a) homopolymer of a monoallylamine whose N atom(s) can form acid addn. salt; (b) homopolymer of a monoallylamine whose N atoms occur as quat. ammonium gps.; (c) homopolymer of a diallylamine whose N atom(s) can form acid addn. salt; (d) homopolymer of a diallylamine whose N atoms occur as quat. ammonium gps.; (e) copolymer of monomer of (a) and/or (b) with (c) and/or (d) and/or (g) triallylamine whose N atom(s) can form acid addn. salt and/or (h) triallylamine whose N atom(s) occur as quat. ammonium gps.; or (f) copolymer of monomer (a) and/or (b) and/or (c) and/or (d) and/or (g) and/or (h) with other copolymerisable. USE/ADVANTAGE - Pretreatment of substrates (claimed), partic. textile materials, esp. cotton, opt. mixed with other fibres. (I) permit shorter dyeing times and greater dyestuff pickup; even dyeing, foularding, and printing is obtd. with mixts. of fibres such as cellulose and small proportion of polyester, better fastness is obtd. on printing.

Description

The invention relates to a mixture with synergistic properties, containing as active components a polymeric compound (P₁), a polymeric compound (P₂) and a textile auxiliary (T), wherein
(P₁) a polymeric compound obtained by reacting epihalohydrin or a precursor of epihalohydrin with a polyalkylene polyamine,
(P₂) a polymeric compound which

• a) a water-soluble homopolymer of a monoallylamine, the N atom (s) can form an acid addition salt,
• b) a water-soluble homopolymer of a monoallylamine, the N atoms are present as quaternary ammonium groups,
• c) a water-soluble homopolymer of a diallylamine, the N atom (s) can form an acid addition salt,
• d) a water-soluble homopolymer of a diallylamine, the N atom (s) are present as quaternary ammonium groups,
• e) a water-soluble copolymer of monomers a) and / or b) with c) and / or d) and / or g) triallylamine, the N atom (s) of which Can form acid addition salt, and / or h) triallylamine, whose N atom (s) exist as quaternary ammonium groups.
• f) a water-soluble copolymer of monomers a) and / or b) and / or c) and / or d) and / or g) and / or h) with others any copolymerizable monomers and

(T) a reaction optionally neutralized with an acid mixture made by

• a) reacting epihalohydrin with ammonia and reacting with epihalohydrin or
• b) reacting epihalohydrin with methylamine or dimethyl amine to a polymer with a molecular weight (in the form a base) of 500-10,000,

is.

The components P₁, P₂ and T are advantageous at temperatures of Mixed 20-50 ° C. P₂ is advantageously mixed with T and then with P₁.  

Good mixtures (M) contain 95 to 10 parts of a polymeric compound (P₁) and 5 to 90 parts of the sum of the products (P₂) plus III (T) each as Active substance in particular 40-50 parts of a compound (P₁) and 60-50 Parts of the sum of the products (P₂) plus (T) each as active substance. Good mixtures (M) contain as a proportion of the sum of the products (P₂) plus (T), 30 parts P₂) and 70 parts T), and advantageously 40 parts P₂) and 60 Parts T) and in particular 50 parts P₂) and 50 parts T) each as Aktivsub punch.

A good mixture (M ') contains a compound (P₁'), a compound (P₂ ') and a textile auxiliary (T'), wherein

P₁ ') a polymeric compound obtained by reacting Epi chlorohydrin with a polyalkylene polyamine of the formula

or a polyalkylene polyimine of the formula

wherein

n is a number from 1 to 5,
R₀ independently of one another is a (2-6C) -alkyl radical,
R₁ independently of one another are hydrogen, a (1-4C) -alkyl radical which is optionally substituted by OH, halogen, phenyl or (1-4C) -alkoxy or a phenyl radical,
R₃ is hydrogen, a (1-22C) -alkyl radical or a (2-22C) - alkenyl or alkynyl radical,
R _{3a is} hydrogen or (1-4C) alkyl,
R₁₅ independently of one another (2-4C) alkylene,
R₁₆ independently of one another are hydrogen or a group of the formula - (R₁₅-NH) _y -H, and
x and y represent numbers such that the molecular weight of the compounds of the formula II is between 300 and 70,000,
R₂ ') is a polymeric compound which is a
2a) or 2b) homopolymer of a monoallylamine, or a
2c) or 2d) homopolymer of a diallylamine, or a
2e) copolymer of a monoallylamine and a diallylamine and optionally a triallylamine, or a
2f) copolymer of a monoallylamine and any other copolymerizable monomer, or a
2i) copolymer of a diallylamine and any other copolymerizable monomer, or a
2k) copolymer of a triallylamine and any other copolymerizable monomer, or a
2l) copolymer of a monoallylamine and a diallylamine and a triallylamine and any other copolymerizable monomers, and
T ') an optionally neutralized with a mineral acid product of a 2-step reaction, obtained by
1) reacting epihalohydrin with aqueous ammonia at temperatures of 50-90 ° C., a molar ratio of 4 mol of epihalohydrin to 8-10 mol of ammonia being used at the start of the reaction and
2) reacting the product obtained under 1) after removing the excess ammonia with 0.1 to 0.5 mol of epi halohydrin.

A particularly good mixture (M '') contains a compound (P₁ ''), a Compound (P₂ ′ ′) and a textile auxiliary (T ′), wherein P₁ ′ ′) is a compound obtained by reacting a compound of formula

wherein

R₃ '(1-4C) alkyl and
R _3a 'is hydrogen or (1-4C) alkyl, in particular a compound of the formula

(CH₃) ₂N-C₃H₆-NH₂ (IV)

with epichlorohydrin
P₂ '') a polymeric compound which
2a) a water-soluble homopolymer of a monoallylamine of the formula

or an acid addition salt thereof, or
2b) a water-soluble homopolymer of a monoallylamine of the formula

or
2c) a water-soluble homopolymer of a diallylamine of the formula

or an acid addition salt thereof, or
2d) a water-soluble homopolymer of a diallylamine of the formula

or
2e) a water-soluble copolymer of V) and / or VI) with a monomer VII and / or VIII or with a monomer IX of the formula

or an acid addition salt thereof and / or a mono mer of the formula

or
2f) a water-soluble copolymer of V and / or VI and / or VII and / or VIII and / or IX and / or X with any other copolymerizable monomer, wherein in the formulas V, VI, VII, VIII, IX or X ,
R independently of one another are hydrogen or methyl,
R₁₀ and R₁₁ independently of one another are hydrogen, (1-4C) -alkyl, benzyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl or cyclohexyl,
R _1a , R _2a , R₁₃ and R₁₄ independently of one another (1-4C) alkyl, cyclohexyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl or benzyl and
A⊖ is an anion and
R₁₀ and R₁₁, or R _1a and R _2a or R₁₃ and R₁₄ together with the N atom bonded to them can form a piperidine, morpholine, pyrrolidine ring.

The products P₁), P₂) and T) can form acid addition salts, in particular special of mixtures, e.g. As hydrochloric acid or phosphoric acid, also from organic acids, e.g. B. formic acid, acetic acid, lactic acid, lemons acid, glycolic acid or methanesulfonic acids etc.

A preferred product T) is the product T '') obtained by unsetting in stage 1) of 4 moles of epichlorohydrin with 9 moles of ammonia and crosslinking the product obtained in stage 1) in stage 2) with 0.3-0.5 mol, in particular 0.4 mol of epichlorohydrin and advantageous neutralization of the product obtained with a mineral acid, especially sulfuric acid.  

Another object of the invention is a method for dyeing, Fou larding, printing or optically brightening nitrogen, thiol or Substrates containing hydroxyl groups, characterized in that pretreated the substrates with a mixture (M) and then with an anionic, basic or sulfur dye, padded or printed or brightened with a brightener.

Textile materials, in particular cotton, are particularly suitable as substrates to understand, but leather can also be pretreated with a mixture (M) will.

Polymeric compounds (P₁) are from the German published application 34 46 282 known. Products not mentioned there can be used according to the Methods mentioned disclosure are manufactured.

The polymeric compounds (P₂) are known per se, for. B. in ver European patent applications Nos. 1 40 309, 1 45 220, 95 233 or 1 42 337 or in published Japanese patent applications messages Nos. 51-57 793, 56-9999, 56-53 292, 56-1 34 284, 57-11 288, 57-82 591, 57-92 012, 60-7079, 45-1457, 49-31 631.

A particularly suitable compound (P₂) is a water-soluble homo polymer of diallylamine made by polymerizing diallylamine or its acid addition salts by means of initiators which are an azo group and contain a group with cationic nitrogen in the presence of a regulator, the homopolymer of diallylamine in the form thereof Hydrochloride in water with a concentration of 55% to 65% by weight a viscosity of 500 mPa · s (Brookfield, spindle No. 4, 100 rpm) to 10,000 mPa · s (Brookfield, spindle No. 4, 10 rpm), in particular a its solution in water with a concentration of 20 wt .-% to 30 Wt .-% a viscosity of 50 mPa · s (Brookfield, spindle No. 3, 100 rpm) up to 2000 mPa · s (Brookfield, spindle No. 4, 100 rpm). Such  Products are known in DOS 37 20 508. The textile auxiliaries (T) are known commercial products, they can be ge according to Example 3.

The pretreatment of the substrates can be carried out according to methods known per se follow e.g. B. after the exhaust process, padding process, but specifically in the continuous process.

After a simple drying process, the active ingredients on the Fiber fixed so that a subsequent dyeing is possible and a above average dye absorption results. As dyes come all known water-soluble dyes in question, especially reactive dyes or substantive dyes, in particular reactive are suitable dyes that are usually insufficiently absorbed on the fiber and when Staining requires a relatively large amount of electrolyte and long staining times. The pretreated and dyed, padded or printed textile material can, if desired, with a fixative according to known Methods are treated. Such fixatives are, for example the mixture (M) itself, or products as disclosed in the PCT Scripture 81/2423 as end products according to claim 1 or as preliminary products A), d. H. without further reaction with an N-methylol compound with a Catalyst according to claim 1, d. H. in principle implementation of a connection of formula III with cyanamide or dicyandiamide (see section 1 of Example 1) are described; other such fixatives are in the DOS 31 37 404, 32 16 913, 33 30 120.

The advantages of the method according to the invention are the shortened dyeing times with pre-treated fibers; therefore after the pad batch Process work, furthermore you achieve a significantly increased color fabric absorption.

Pretreating the fibers also has the advantage of being non-homogeneous dyeable substrates, such as. B. when mixed with dead cotton or So-called "mini blends", where in addition to the predominant proportion of cellulose smaller amounts of synthetic fibers, e.g. B. polyester, are fiction  can be dyed, padded or printed in any way and homogeneously. The pretreatment also results when printing with water-soluble dyes textiles improved fastness properties.

The pretreatment is carried out in space using the pull-out or padding process common at a pH of 4-14, especially 7 to 14 and in particular 10 to 14 through. Pretreatment in the exhaust process becomes advantageous at temperatures between 20-90 ° C, advantageously between 30-60 ° C led, using 1 to 20 and advantageously 1-6% of the 100% Active products P₁), P₂) and T) calculated on the fiber weight.

In foulard pretreatment, 10-100 g / l and especially are used advantageously 30-70 g / l of 100% active product of the mixture M), in particular with a squeezing effect of approx. 60-80%.

The textile material is with a substantive dye or a Di rect dye, di- or triphenylmethane dye, phthalocyanine, Formazan or indigo dyed, padded or printed. For this one advantageously uses at least two SO₃H groups or sulfone substantive dye containing amide groups or a direct dye substance, in particular one of 3 to 8 and advantageously 4 to 6 SO₃H- or Contains sulfonamide groups. Highly substantive direct are advantageous dyes used, which according to known exhaust dyeing processes colors also have the properties that they have an extract value of 70-100% and preferably 80-100%, this with boiling dyeing in a ¹ / ₁ standard strength.

Preferred substantive dyes or direct dyes with planarcha characters have a molecular weight of 900 to 1200 and are special 1: 1 or 1: 2 metal complexes, especially copper complexes.

It is advantageous to use a substantive dye or a direct one dye, the one or more, for example 1 to 3 and preferred one or two and particularly preferably two residues of a 5 or 6 member preferably heterocyclic ring with aromatic character  2 or 3 N atoms, which heterocyclic ring by 1 to 3 halogen atoms, especially chlorine or fluorine, is substituted.

Of these dyes, those which have one are particularly preferred or two residues of mono- or dihalo, preferably chlorine or fluorine and in particular have chlorotriazinyl residues. Such preferred Di rect dyes are described in DOS 34 46 282 and can be invented be used properly.

Other suitable dyes are from PCT published application 81/2423 or from DOS 31 37 404, 32 16 913, 32 28 286, 32 44 999 or 33 20 972 known, or can according to that described in DOS 32 03 548 Test methods can be determined as suitable. Such dyes are known as CI Direct Dyes.

The pretreated textile material can also be dyed, padded or printed with a reactive dye, in particular with reactive dyes which have the remainder of a 5- or 6-membered heterocyclic ring with an aromatic character, preferably having 2 or 3 N atoms, which ring is heterocyclic 1 to 3 halogen atoms is substituted, which are split off as an anion during dyeing. The reactive residue in such dyes can also be a vinylsulfonyl, vinylcarbonyl, sulfato, mono- or dichloroquinoxaline or sulfuric acid ester residue. Such dyes are known as CI Reactive Dyes, e.g. B. from PCT-Offenlegungsschrift 81/2423 or DOS 31 37 404, 32 16 913. Suitable dyes that dye, padding or printing pretreated natural or synthetic polyamides by known methods are the so-called. CI Acid Dyes, ie acid - or nylon dyes and are known in particular from the following patents:
DP 16 44 356, DP 20 13 783, DP 21 53 548, DOS 22 02 419, DOS 24 00 654, DOS 26 31 830, DOS 27 29 915, DOS 30 34 576, FP 75 06 109, FP 76 24 658.

The pretreated textile material can also be treated with a phthalocyanine, Dye vat, formazan, di or triphenylmethane or indigo dye, padding or printing or with sulfur dyes, as in the DOS 35 33 383 are known.

Suitable, if appropriate, basic dyes containing sulfonic acid groups, which dye substrates which can be base-dyed by a known method, foular dieren or printing are known as CI Basic Dyes and contain pro tonable primary, secondary, tertiary amino groups and / or quaternary Ammonium groups.  

Manufacture of the products Example 1 (polymeric compound P 1)

472 parts of dimethylaminopropylamine are placed in a vessel and 1350 parts of water, advantageously demineralized, with cooling Water, added, the temperature of the solution being 25 ° C. To obtained solution are at a temperature of 25-30 ° C in the course of 428 parts of epichlorohydrin were added dropwise in 3-4 hours. After the whole por tion epichlorohydrin has been added, 390 parts are then added Add 30% hydrochloric acid in the course of 1 to 2 hours, the tem temperature of the solution is kept 25-30 ° C. To prevent gel formation, should the addition of hydrochloric acid after the complete addition of Epichlorohydrin should be done as quickly as possible. The pH of the solution is 6.5-7.0. To complete the reaction, the mixture is heated to 70 ° C. and heated with stirring at 70-75 ° C for 3 hours.

After this time the mixture is cooled to 40 ° C and added brought from 115 parts of hydrochloric acid to a pH of 4.5 to 5.0. The active product thus obtained dissolved in water can be used directly.

Example 2 (polymeric compound P₂) (see DOS 37 20 508)

a) 193.9 parts of diallylamine hydrochloride solution with a concentration of 68.85% with 8.2 parts of phosphorous acid with constant Passing nitrogen through heated to 65 °. Then will a solution of 3.5 parts of 2,2'-azo-bis- (2-amidinopropane) dihydro chloride in 19.8 parts of water evenly within 19 hours added. The mixture is stirred for a further 21 hours at 65 ° and then open heated to approx. 95-100 °, stirred for 2 hours and cooled.

The 59.2% polymer hydrochloride has a viscosity of 1540 mPa · s (Brookfield, spindle No. 4, 50 rpm).

By quickly stirring in 142 parts of 30% sodium hydroxide solution Polyamine base can be released easily. 367 parts are obtained  Polyamine solution with a concentration of 26.4%. The viscosity is 630 mPa · s (Brookfield, spindle 4, 100 rpm).

b) The procedure is as in Example a), but the amount of phosphorous acid reduced to 4.1 parts, a polymer hydrochloride of 60.3% is obtained with a viscosity of 2950 mPa · s (Brookfield, spindle No. 4, 20 rpm). If this product is diluted with 215 parts of water and with 265.2 parts of 30% sodium hydroxide solution released the polymer base a 21% solution with a viscosity of 225 mPa · s (Brook field, spindle no.3, 100 rpm).

c) 498.7 parts aqueous allylamine hydrochloride solution of 75% and 793.5 Parts of diallylamine hydrochloride solution of 67.3% are presented and inerted with nitrogen. Subsequently, nitrogen is added device heated to 65 ° C. At this temperature is under good Stir ¹ / ₁₀ a prepared 15% solution of 31.5 parts 2,2'-azo-bis- (2-amidinopropane) dihydrochloride in 178.5 parts water admitted. The polymerization is exothermic and is between Kept at 65-75 ° C. After exothermia has subsided, but at the earliest after Another tenth of the initiator solution is added for 1.5 hours. After about four times ¹ / ₁₀ addition there is practically no exotherm on. After the last addition of initiator, the mixture is left at 75 ° C. for 3 hours stirred and then cooled. The solution obtained is still with 1066.5 parts of sodium hydroxide solution, neutralized approx. 30% and with Diluted 181.3 parts water. 2750 parts of a viscous are obtained Liquid containing 22.4% free polyamine.

d) 1000 parts of a 70% aqueous monoallylamine hydrochloride solution are with 17.5 parts of 2,2'-azo-bis- (2-amidinopropane) in 37.5 Parts of water dissolved as follows:

• - After inerting with nitrogen and warming up to 50 ° C 27.5 parts of initiator solution added  
• - after 30 hours of polymerization, the second portion Initiator solution added (27.5 parts).

After a total polymerization time of 60 hours, the polyallylamine Hydrochloride by precipitation in methanol as anhydrous, 100% Powder isolated.

Example 3 (Textile Aid T)

370 parts of an 8.4% ammonia solution are placed under nitrogen atmosphere at a temperature of 60 ° C with 76 parts epichlorohydrin reacted and stirred for 2-3 hours while the tem temperature is kept at 60-65 ° C. The mixture is at 1 hour at 60-65 ° C held and then at 90 ° C for 5 hours.

At a temperature of 100 ° C 25-30 parts of aqueous ammonia distilled solution, the solution cooled to 20 ° C and 85 parts of a 30% aqueous soda solution added and then another 90-100 parts the aqueous ammonia solution is distilled off under vacuum at 60-70 ° C until all ammonia is distilled off.

50 parts of water and 7.7 parts are obtained at 30 ° C. to the product obtained Epichlorohydrin added and stirred for 1 hour, cooled and at a pH of 6.5-7.5 with 23 parts of 65% sulfuric acid; 30% by weight of the active substance is obtained by adding water as salt.

Example 4 (polymeric compound P₂)

228 parts of allylamine are cooled to 5-10 ° C. and with external cooling slowly added 389 parts of 37% hydrochloric acid. Under stick At 70 ° C, the material atmosphere becomes 14 parts within 20 hours 2,2'-azo-bis- (2-amidinopropane) dihydrochloride in 80 parts of water continuously admittedly. After 10 hours of stirring, the temperature will still increase Increased to 90 ° C for 2 hours and then the mixture cooled. Man receives 711 parts of polyallylamine hydrochloride solution containing 52.6% of polymer allylamine hydrochloride, which is 32% of free polyallyl corresponds to amine base.

Mixture A
Synergistic mixture consisting of:

100 parts of the product from Example 1 (polymeric compound P₁),
50 parts of the product from Example 4 (polymeric compound P₂),
50 parts of the product from Example 3 (textile auxiliary T).

First, 50 parts of the polymeric compound P₂ with 30-35% active substance submitted with stirring at temperatures between 20-40 ° C and with Treated 50 parts of a compound from Example 3 until one clear, stable solution is obtained (mixture Z). Then 100 Parts of the product from Example 1 with 100 parts of the mixture Z cold to mixed for clarification. A yellow liquid with a density is obtained at 20 ° C from 1.07-1.090. The pH of the aqueous solution is between 4.0-4.5. The mixed product is clearly mixed in cold water bar.

Application example 1 (1st continuity method)

A cotton fabric (cretonne) is made with a solution consisting of 100 g / l the mixture A) whose pH is 12 (with an aqueous sodium hydroxide solution adjusted) pretreated. After fouling with one Squeezing effect of about 80%, the fabric is dried at 120 ° C. The fabric pretreated in this way can be used directly without being neutralized Reactive dye can be dyed by known methods, e.g. B. with a 3% coloring of the reactive dye of Example 5 of the US patent 44 75 918.

The color depth of the coloring is significantly higher compared to wet fastness properties of comparative dyeings on cotton with the same color fabric, either with the products P₁) or P₂) or T) alone were treated.  

Application example 2 (pretreatment in the exhaust process)

The pretreatment on a 100% cotton fabric is carried out on one Reel runner. You go in with the fabric at a temperature of 20-25 ° C a bath containing 2-3% of the active substance of mixture A (on 100% active calculated fabric) and based on the weight of the goods. The bathroom will heated to 40 ° C and then added within 10-15 minutes brought to a pH of 10 by sodium carbonate. Afterwards adjust the bath to a pH of 12 by adding a aqueous sodium hydroxide solution within 5 minutes. At 40 ° C and at a pH of 12 the bath is treated for a further 15 minutes, with the total duration of treatment is about 30 minutes. The so pretreated The fabric is then rinsed warm and cold and neutralized with acetic acid siert and dried.

The cotton fabric pretreated according to application examples is included 40 g / l of the dye of the formula

Padded using the pad-patch method, rolled up for 30 minutes Allow to linger, then rinsed hot and cold, boiling for 15 minutes soaped and processed according to known methods. When dyeing no other additions such as ammonium sulfate, sodium chloride or Alkali. The colorations obtained gave deeper shades than coloring without pretreatment, or with the individual products alone pre-treated cotton.

Claims (15)

1. Mixture (M) with synergistic properties, containing as active components a polymeric compound (P₁), a polymeric compound (P₂) and a textile auxiliary (T), wherein (P₁) is a polymeric compound obtained by reacting epi halogenohydrin or one Precursor of epihalohydrin with a polyalkylene polyamine,
(P₂) a polymeric compound which

• a) a water-soluble homopolymer of a monoallylamine, the N atom (s) of which can form an acid addition salt,
• b) a water-soluble homopolymer of a monoallylamine, the N atoms of which are present as quaternary ammonium groups,
• c) a water-soluble homopolymer of a diallylamine, the N atom (s) of which can form an acid addition salt,
• d) a water-soluble homopolymer of a diallylamine, the N atom (s) of which are present as quaternary ammonium groups,
• e) a water-soluble copolymer of monomers a) and / or b) with c) and / or d) and / or g) triallylamine, the N atom (s) of which can form an acid addition salt, and / or h) triallylamine, the N -Atom (s) are present as quaternary ammonium groups.
• f) is a water-soluble copolymer of monomers a) and / or b) and / or c) and / or d) and / or g) and / or h) with any other copolymerizable monomers and

(T) a reaction mixture optionally neutralized with an acid, prepared by

• a) reacting epihalohydrin with ammonia and reacting with epihalohydrin or
• b) reacting epihalohydrin with methylamine or dimethylamine to form a polymer with a molecular weight (in the form of a base) of 500-10,000,

is. 2. Mixture (M) according to claim 1, containing 40-50 parts of a Ver bond (P₁) and 60-50 parts of the sum of the products (P₂) plus (T) each as Active substance. 3. Mixture (M) according to claims 1 and 2, containing as a proportion of Sum of the products (P₂) plus (T), 30 parts (P₂) and 70 parts (T), before some 40 parts (P₂) and 60 parts (T) and especially 50 parts (P₂) and 50 parts (T) each as an active substance. 4. Mixture (M ') according to claim 1, containing a compound (P₁'), a compound (P₂ ') and a textile auxiliary (T'), wherein P₁ ') is a polymeric compound obtained by reacting epi chlorohydrin with a polyalkylene polyamine of the formula or a polyalkylene polyimine of the formula where a number from 1 to 5,
R₀ independently of one another is a (2-6C) alkylene radical,
R₁ independently of one another are hydrogen, a (1-4C) alkyl radical which is optionally substituted by OH, halogen, phenyl or (1-4C) alkoxy or a phenyl radical,
R₃ is hydrogen, a (1-22C) -alkyl radical or a (2-22C) - alkenyl or alkynyl radical,
R _{3a is} hydrogen or (1-4C) alkyl,
R₁₅ independently of one another (2-4C) alkylene,
R₁₆ independently of one another hydrogen or a group of the formula
- (R₁₅-NH) _y -H mean, and
x and y represent numbers such that the molecular weight of the compounds of the formula II is between 300 and 70,000,
P₂ ′) is a polymeric compound which is a
2a) or 2b) homopolymer of a monoallylamine, or a
2c) or 2d) homopolymer of a diallylamine, or a
2e) copolymer of a monoallylamine and a diallylamine and optionally a triallylamine, or a
2f) copolymer of a monoallylamine and any other copolymerizable monomer, or a
2i) copolymer of a diallylamine and any other copolymerizable monomer, or a
2k) copolymer of a triallylamine and any other copolymerizable monomer, or a
2l) copolymer of a monoallylamine and a diallylamine and a triallylamine and any other copolymerizable monomers, and
T ') an optionally neutralized with a mineral acid product of a 2-step reaction, obtained by
1) reacting epihalohydrin with aqueous ammonia at temperatures of 50-90 ° C., a molar ratio of 4 mol of epihalohydrin to 8-10 mol of ammonia being used at the start of the reaction and
2) Reacting the product obtained under 1) after removing the excess ammonia with 0.1 to 0.5 mol of epihalohydrin. 5. Mixture (M '') according to claim 1, containing a compound (P₁ ''), a compound (P₂ '') and a textile auxiliary (T '), wherein P₁'') a compound obtained by reacting a compound of formula whereinR₃ '(1-4C) alkyl and
R _3a 'is hydrogen or (1-4C) alkyl, in particular a compound of the formula (CH₃) ₂N-C₃H₆-NH₂ (IV) with epichlorohydrin,
P₂ '') a polymeric compound which
2a) a water-soluble homopolymer of a monoallylamine of the formula or an acid addition salt thereof, or
2b) a water-soluble homopolymer of a monoallylamine of the formula or
2c) a water-soluble homopolymer of a diallylamine of the formula or an acid addition salt thereof, or
2d) a water-soluble homopolymer of a diallylamine of the formula or
2e) a water-soluble copolymer of V) and / or VI) with a monomer VII and / or VIII or with a monomer IX of the formula or an acid addition salt thereof and / or a monomer of the formula or
2f) a water-soluble copolymer of V and / or VI and / or VII and / or VIII and / or IX and / or X with any other copolymerizable monomer, wherein in the formulas V, VI, VII, VIII, IX or X
R independently of one another are hydrogen or methyl,
R₁₀ and R₁₁ independently of one another are hydrogen, (1-4C) -alkyl, benzyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl or cyclohexyl,
R _1a , R _2a , R₁₃ and R₁₄ independently of one another (1-4C) alkyl, cyclo hexyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl or benzyl and
A⊖ is an anion and
R₁₀ and R₁₁, or R _1a and R _2a or R₁₃ and R₁₄ together with the N atom bonded to them can form a piperidine, morpholine, pyrrole din ring. 6. Process for dyeing, padding, printing or optically brightening of textile materials containing nitrogen or hydroxyl or thiol groups rial, characterized in that the textile material with a Mixture (M) pretreated according to claim 1 and then with a dyes, padded or anionic or basic or sulfur dye printed or brightened with an optical brightener. 7. Use of the mixture (M) according to claim 1 for pretreating Substrates.   8. Use of the mixture according to claim 1 for the pretreatment of Tex Style materials, especially cotton alone, optionally in a mixture with other fibers. 9. Use of the mixture (M) according to claim 1 for the pretreatment of Textile material in an amount of 10-100 g / l, advantageously 30-50 g / l dyeing liquor based on 100% active substance. 10. Use of the mixture (M) according to claim 1 for the pretreatment of Textile material in the drawing process in an amount between 1-20% partial between 1.5-10% with a fleet ratio of 1: 5 to 1:30. 11. The method according to claim 8, characterized in that the textile material is a mixture of cotton and polyester and the dyeing One bath process is using a dispersion and a reak tive dye. 12. The substrate pretreated with a mixture (M) according to claim 1. 13. The textile material dyed according to claim 6.